Bismuth sodium titanatebarium titanate [(1-x)(Na1/2Bi1/2)TiO3-xBaTiO3, NBT-100xBT] is one of the most well studied lead-free piezoelectric materials due in large part to the high field-induced strain attainable in compositions near the morphotropic phase boundary (x = 0.06). The BaTiO3-rich side of the phase diagram, however, has not yet been as comprehensively studied, although it might be important for piezoelectric and positive temperature coefficient ceramic applications. In this work, we present a thorough study of BaTiO3-rich NBT-100xBT by ferroelastic measurements, dielectric permittivity, X-ray diffraction, and Raman spectroscopy. We show that the high-temperature mechanical behavior, i.e., above the Curie temperature, TC, is influenced by local disorder, which appears also in pure BT. On the other hand, in NBT-100xBT (x<1.0), lattice distortion, i.e., tetragonality, increases, and this impacts both the mechanical and dielectric properties. This increase in lattice distortion upon chemical substitution is counterintuitive by merely reasoning on the ionic size, and is due to the change in the A-O bond character induced by the Bi3+ electron lone pair, as indicated by Raman spectroscopy. (C) 2015 AIP Publishing LLC.